Unsaturated furoate



Patente Mar. 2 1940 No ."Drawing;

1 The'present invention relates to new unsaturatedfuroates having the generaliormula'zw v I Hal-:1

whereinY-represents a hydrocarbon radical con taining at 'least-o'ne e'thylenic'linkage in an aliphatic chain. These'new compounds are allcolorless mobile liquids with moderatatel'y high boiling points. They are usefulas solvents for various materials and especially as modifying agents in the polymerization oi vinyl compounds,

particularly styrene. I

The new' esters may be pr'epared byreacting:

, furoic'acid with-analcoholbontaining at least one ethylenic linkage. Thereaction is preferably carried out using approximatelyone mol 'of furoic acid, an excess, e. g. 1.1'to 5mo1s, of'the at cohol, and a small proportion, e. g. 0.01to 0.1

mol, of a mineral acid as a catalyst, although other proportions may be used. The agents are mixed and heated at a moderate temperature, e. g. 40 to 150 C.,]for a'period of from about '4 to 30 hours. Excess alcoholis' then distilled from the mixture, after which the residue is neutralized andifractionally di'stilled at reducedpressure to separate the; ester' product. i

In preparingunsaturated furoates by the'method just described, I have found that the yield may be improved byadding to the esterification' mixture a water-immiscible liquid which forms an azeotropic mixture with water. As the reaction proceeds, the azeotrope may be boiled off, thus removing the water formed during" the esterification and allowing the reaction to proceed more nearly to completion. Methylene dichloride and chlorobenzene have been found particularly suitable ior this purpose.

pared by reacting a heavy metal salt, e. g. a lead and silver salt, of furoic acid with a hydrocarbon halide containing at least one ethylenic'linkage. According 'to' the preferred procedure, a mixture of one'mol of the salt and. an excess, e. g. 2 to 10 mols, of the halide is-heated in a closed container for several hours at a temperature between about 100 and 200 C. The reaction mixture is then' coiled, washed with water, and filtered, and the filtrate-is. fractionally distilled at reduced pressure to uct.

.The following examples illustrate various ways: in which the principle of the invention has been employed but are not to be construed as limiting the invention: e e v m ple 1.

A mixture of 112 grams of furoic acid, 84 grams of allyl alcohol, 5 grams of concentratedsulfuric The new unsaturated esters may also be pre C., and having theformula:

separate the esterfprodor Midland, 'Mich., I a j 2 31 gramsof methylene dichloride was heated for 22,.h0urs at a temperature betweenv about 45C. and about 0. During thistime,

the methylene .dichloridewwater azeotrope distilled; slowly from the: mixture and was* condensed; the-water being separated and the methylene dichloride returnedgto the reaction.- 'Inall 1- 5 .5 ,grams.-,of.water' was thus separated; When thereaction was complete, sodium carbonate was added agto'neutralize the mixture, and the latter wasthen fractionally distilled at reduced pres- 1619 1 1;flflGfiiQRdEtiH at t peratur s" be;

at 0.15 inch being collected. This fraction consisted of 113 grams of allyl iuroate, the formula Allyl furoate is a colorless mobile liquid having a specificigravity of 1.118 at 25/25 C. and a refractive index of 1.4945 at 20 C.

Example 2' A mixture of i12 grams of furoic ,acid, 186

grams'o-f geraniol, 1 gram of concentrated sulfuric acid and 300 grams of chlorobenzene was heated for 22 hoursfat temperatures-between 147 and 154 C. During heating, the chlorobenzene-water azeotrope distilled slowly from the mixture and was condensed, the water being separated and the 'chlorobenzene returnedccntinuously to. the reaction." In all 18 grams of water was thus removed. I When the reaction was complete, sodium carbonate was added to neutralize the mixture and the latter Wasfrac- 1 tionally distilled at. reduced pressure, the fraction distilling at temperatures between 148 and 155 at 0.2 inch absolute pressure being collected. This fraction consisted of 89 grams of geranyl furoate, a slightly yellowish sweet-smelling liquid having a specific gravity of 0.975

A mixture .of, 81 grams .of lead furoateand 135.7 grams of methallyl chloride was h'eated 'in cooledgwashed with water, and filtered. The

"tween 81 at 0.2 inch absolute pressure, and 82 15,,

a closed container for 4hours at a temperature of about C. The reaction mixture was then filtrate was fr'actionally distilled at reduced presf sure, the fraction'distilling at' temperatures between 82 and 84 C; at 0.1 inch absolutepressure being collected. This fraction consists of 11 The product is a colorless mobile grams of methallyl furoate, which has theformula: I

HCCH 0 on: V

g p HG C-C-OGHz-C=CH2 aspecific gravity of 1.086 at 25/25 and a refractive index of 1.4922 at 20. C. 10

Other furoates having the general formula hereinbefore presented may also be prepared by the methods illustrated in the foregoing detailed examples, e. g. crotyl furoate, (penten-1-y1-5) HC-CH o H ll a no C-COY wherein Y represents a hydrocarbon radical containingat least one ethylenic linkage in an aliphatic chain.

liquid having formula 2. An unsaturated iuroate having the general formula: v HUI-{1H wherein R is an aliphatic radical containing at least one ethylenic linkage.

3. Allyl furoate, a colorless mobile liquid having a boiling point of about 81?.at 0.2 inch absolute pressure; a specific "gravity of about 1.118 at 25725? C., and a refractive index of about 1.4945 at 20 c. i p p 4. Methallyliuroate, a colorless mobile liquid having a boiling point of about 82 to 84 C. at 0.1 inch absolute'pressure, a specific gravity of about 1.086 at 25/25 C. and a. refractive index of about1A=922 at 20 C. Z

5. Geranyl furoate, a slightly yellowish sweetsmelling liquid,- having a, boiling point of about 148 to 153- C. at 0.2 inch absolute pressure, and a specific gravity of about.0.975 at 25/25 C.

6. An unsaturated furoate having the general wherein Y is a radical selected from the class 

